KR20020048670A - Flame retardant polyolefine resin composition - Google Patents

Abstract

PURPOSE: Provided is a fire retardant polyolefin resin composition which has excellent light resistance and does not show discoloration by combining tris(brominated neopentyl) phosphate, antimony trioxide and N-OR-substituted hindered amine compound. CONSTITUTION: The polyolefin resin composition comprises 100 parts by weight of polyolefin, 0.1 to 50 parts by weight of tris(brominated neopentyl) phosphate, 0.1 to 20 parts by weight of antimony trioxide and 0.01 to 5 wt% of a hindered amine compound substituted with N-OR. The polyolefin may be polypropylene. The tris(brominated neopentyl) phosphate possess at least one selected from the group consisting of tris(tribromo neopentyl) phosphate, tris(dibromo neopentyl) phosphate and tris(monobromo neopentyl) phosphate. The hindered amine compound substituted with N-OR may be a compound of the structure represented by the formula 1 or 2.

Description

Flame retardant polyolefin resin composition {FLAME RETARDANT POLYOLEFINE RESIN COMPOSITION}

The present invention relates to a flame retardant polyolefin resin composition, and more particularly to a flame retardant polypropylene resin composition having excellent light resistance and no discoloration.

BACKGROUND ART [0002] Non-combustible resins, flame retardant resins, or self-fired resins are conventionally used for the purpose of preventing ignition, combustion, or fire generated from electrical troubles. For this reason, since olefin resins, especially polypropylene, made from hydrocarbons are excellent in impact properties, rigidity, appearance and formability, various proposals for flame retardation have been made here. In the flame retardancy standards of electrical appliances, the United States UL standard (UL94) requires a high degree of flame retardancy depending on the product or part, so export products to the United States is required to select a material that meets the UL standard. In response to these demands, many materials using organic and inorganic flame retardants and flame retardant aids for thermoplastic polyolefin resins have been proposed, and decabromo diphenyl ether, brominated bisphenol S derivatives and brominated bisphenol derivatives are mainly used. On the other hand, parts exposed to the sun when exposed to the sun or irradiated with fluorescent lamps or mercury lamps require light resistance. Therefore, various light stabilizers such as benzotriazole-based, benzoate-based, and hindered amine-based compounds are applied to polyolefins. The compounding use improves light resistance. However, when a flame retardant is blended with polyolefin for the purpose of imparting flame retardancy, even if a weather stabilizer is blended to impart weather resistance, the improvement of weather resistance can not be expected greatly. At this time, even if the amount of the weather stabilizer is increased, a large improvement is expected. it's difficult. In addition, even when the hindered amine compound is not used in combination with a general flame retardant itself, the resin discoloration problem occurs in combination when used in combination is a cause that seriously inhibits the efficacy of the flame retardant. Such countermeasures include tris (neobromyl bromide) phosphate, antimony trioxide, and bis (2,2,6,6-tetramethyl 4-piperidyl) sebacate and bis (1,2,2,6,6) in polyolefins. A resin composition having both flame retardancy and light resistance is proposed by combining a light stabilizer of an N-hydrogen hindered amine compound which is not substituted with a nitrogen atom such as pentamethyl 4-piperidyl) sebacate. Light resistance under high energy is insufficient (Japanese Patent Laid-Open No. 6-136188). There are also proposals to incorporate light stabilizers of tris (bromide neopentyl) phosphate, antimony trioxide, and N-alkyl-substituted hindered amine compounds to improve the light resistance, but these also exhibit poor light resistance and insufficient light resistance under high energy. ( Japanese Patent Laid-Open No. 8-109287).

The present inventors have studied in view of the above problems, and when the tris (neobromide bromide) phosphate, antimony trioxide and N-OR substituted hindered amine compound is blended with polyolefin, high flame retardancy, high light resistance and discoloration resistance can be obtained. Knowing that the present invention has been proposed. That is, the present invention is to provide a resin composition having a flame retardancy of V0, V1, V2 in the UL94 standard and at the same time having a high light resistance and discoloration resistance.

The present invention relates to 100 parts by weight of (A) polyolefin (B) 0.1 to 50 parts by weight of tris (neobromide bromide) phosphate, (C) 0.1 to 20 parts by weight of antimony trioxide and (D) 0.01 to N-OR substituted hindered amine compound It provides a flame retardant polyolefin resin composition comprising 5 parts by weight.

The "polyolefin" used in the present invention is a homopolymer of α olefins such as ethylene, propylene, butene 1, pentene 1, hexene 1, blocks, random and graft copolymers between the above α olefins, or such homopolymers or copolymers. And mixtures thereof. The above copolymer may be copolymerized with monomers other than alpha olefins such as maleic anhydride and vinyl acetate in a range that does not impair the properties of the copolymer.

As the flame retardant used in the present invention, tris (brominated neopentyl) phosphate is tris (tribromo neopentyl) phosphate, tris (dibromo neopentyl) phosphate, tris (monobromo neopentyl) phosphate, etc. Or it can mix and use. The compounding quantity of tris (bromide neopentyl) phosphate is 0.1-50 weight part with respect to 100 weight part of polyolefins, Preferably it is 2-30 weight part. If the blending amount is smaller than the lower limit, flame retardancy cannot be obtained. If the blending amount is higher than the upper limit, stable kneading and molding operations are difficult, and specific gravity increases and impact resistance decreases, which is not preferable.

Antimony trioxide as the flame retardant aid used in the present invention can be used without particular limitation, but the preferred compounding amount is 0.1 to 20 parts by weight and more preferably 1 to 10 parts by weight with respect to 100 parts by weight of polyolefin. In the case of more than the upper limit, the specific gravity increases and the impact resistance decreases, which is undesirable.

As the light stabilizer used in the present invention, the N-OR-substituted hindered amine compound may be any known compound in which the hydrogen atom bonded to the nitrogen atom included in the hindered amine compound is OR-substituted, without particular limitation. And the compounds shown in (2) are very useful because the light resistance decreases due to the combination with a flame retardant.

In the present invention, the blending amount of the N-OR substituted hindered amine compound is 0.01 to 5 parts by weight, and preferably 0.03 to 3 parts by weight based on 100 parts by weight of the polyolefin. When the blending amount is smaller than the lower limit, sufficient light resistance is not exhibited, and when the blending amount is larger than the upper limit, further light resistance is not improved.

The flame-retardant resin composition of the present invention may be added with known stabilizers, antistatic agents, nucleating agents, lubricants, fillers and the like, if necessary in the range not impairing the effects of the present invention in addition to the above components.

Although an Example and a comparative example are mentioned in order to demonstrate this invention concretely, this invention is not limited to these Examples.

Example

The flame retardancy evaluation carried out in the present invention was based on the UL subject 94 (Underwrites Laboratories Incorporation) "combustibility test of plastic materials for mechanical parts" performed in the vertical phase (V0). The test fraction used was 1/16 inch thick.

The compositions prepared by the present invention were classified as UL94 V0 when the following criteria were met; A set of five specimens of dimensions 127 x 12.7 x 1.6 mm shall be in direct contact with a flame (19 mm high), held twice for 10 seconds each, and then flame burned for at least 10 seconds so that no specimens burn. For 10 sparks applied to each set of 5 specimens, the total flame burn time shall not exceed 50 seconds.

None of the specimens shall be free of spark particles, no flammable or more flammable specimens until clamped, and no flammable specimens lasting more than 30 seconds after the second removal of the test flame.

The classification to UL94 V1 requires that the flame burning time per specimen shall not exceed 30 seconds and that the total flame burning time for 10 flame applications in each set of five specimens shall not exceed 250 seconds. The combustion progress should not last longer than 60 seconds. Other criteria are the same as those mentioned above. Materials with specimens from which spark particles fell while satisfying other criteria for classification of UL94 V1 were classified as UL94 V2.

For the light resistance test, Fluorescent UV-condensation tester based on ASTM D4329 test method was used, and the exposure time was measured under the environment of 83 ℃, and the time and color change until the surface crack occurred, and the color change was ○ discoloration, △ slight discoloration , X discoloration, XX is indicated as severe discoloration. The test piece used the board of thickness 50mmx40mmx2mm.

In order to prepare the flame retardant resin composition of the present invention, the mixing method and the mixing order of each component are not limited, and Henschel mixer, a general tumbler mixer, and the like can be used. In the present invention, the polyolefin, the flame retardant, the flame retardant aid and the light stabilizer were added as 0.1% by weight of calcium stearate and 0.1% by weight of the antioxidant IRGAFOS-168 (trade name: Shivagai Co.) in a Henschel mixer. It stirred and mixed for 3 minutes. The resulting mixture was melted and extruded at 190 ° C using a twin screw stirring extruder having a diameter of 30 mm to prepare pellets. The obtained pellets were dried at 100 ° C. for 3 hours, molded using an injection molding machine having a maximum temperature of 200 ° C. to prepare a specimen for testing flame resistance and light resistance, and flame resistance and light resistance were measured.

Example 1

100 parts by weight of a crystalline polypropylene block copolymer having a melt flow index (melt flow rate of the melt for 10 minutes at 230 ° C. under a load of 2.16 kg) as a polyolefin resin and tris (tribromo neopentyl as a flame retardant) Phosphate (CR-900 (trade name): Daihachi Chemical Co., Ltd.) 15 parts by weight, 7 parts by weight of antimony trioxide (Sb ₂ 0 ₃ W: Best Flame Retardant Co., Ltd., 1.2 μm) as flame retardant aid, N-OR as light stabilizer 0.5 parts by weight of the substituted hindered amine compound (CGL-116 (trade name): Shiva-Geigi Co., Ltd.) was prepared in a specimen according to the above-described preparation method, and flame retardancy and light resistance were measured. The results are shown in Table 1 below.

Examples 2-3 and Comparative Examples 1-7

A fillet was prepared under the same conditions as in Example 1, except that the blending amount of the flame retardant and the flame retardant was replaced with the amount shown in Table 1. The pellets were molded by using an injection molding machine to prepare a test piece, and And the light resistance was measured, and the results are shown in Table 1.

As shown in Table 1, it can be seen that when tris (tribromo neopentyl) phosphate is added in an appropriate range to the resin compositions of Examples 1 to 3 and Comparative Examples 1 to 7, it exhibits excellent light resistance.

Examples 4-6 and Comparative Examples 8-13

A fillet was prepared under the same conditions as in Example 1 except that the compounding amount of the light stabilizer was replaced with the amount shown in Table 2, and the obtained pellets were molded using an injection molding machine to prepare a test piece, and the flame resistance and light resistance It measured, and the result is shown in Table 2.

Excellent flame retardancy when the N-OR substituted hindered amine compound (CGL-116 (trade name): Shiba GIGI) was added as a light stabilizer to the resin compositions of Examples 4 to 6 and Comparative Examples 8 to 13 as shown in Table 2. And discoloration could be obtained.

Example 7

The polyolefin was prepared under the same conditions as in Example 1 except as shown in Table 2. The obtained pellets were molded using an injection molding machine to prepare test pieces, and flame retardance and light resistance were measured. Is shown in Table 2.

Composition evaluation division (A) (B) (C) (D) Flame retardant Light resistance (hours) Light resistance (color change) (A) -1 (A) -2 (B) -1 (B) -2 (B) -3 (B) -4 (B) -5 (D) -6 Example 1 100 15 7 0.5 V0 1,500 ○ Example 2 100 5 2 0.5 V2 1,700 O Example 3 100 30 20 0.5 V-0 1,300 ○ Comparative Example 1 100 15 0.5 HB 1,500 ○ Comparative Example 2 100 7 0.5 HB 1,600 ○ Comparative Example 3 100 25 7 0.5 V0 900 XX Comparative Example 4 100 25 7 0.5 V0 800 XX Comparative Example 5 100 15 7 0.5 V0 600 XX Comparative Example 6 100 15 7 0.5 V0 700 XX Comparative Example 7 100 70 20 0.5 Molding impossible

Composition evaluation division (A) (B) (C) (D) Flame retardant Light resistance (hours) Light resistance (color change) (A) -1 (A) -2 (B) -1 (D) -1 (D) -2 (D) -3 (D) -4 (D) -5 (D) -6 (D) -7 Example 4 100 15 7 VO 700 0 Example 5 100 15 7 VO 2,500 0 Comparative Example 8 100 15 7 VO 100 △ Comparative Example 9 100 15 7 0.5 VO 700 0 Comparative Example 10 100 15 7 0.5 VO 600 0 Comparative Example 11 100 15 7 0.5 VO 900 X Comparative Example 12 100 15 7 0.5 VO 950 X Comparative Example 13 100 15 7 0.5 VO 1,100 △ Example 6 100 15 7 0.5 VO 1,400 0 Example 7 100 15 7 0.5 VO 1,500 0

(A) -1: BJ700 (propylene block copolymer, MFR = 20, Samsung General Chemical)

(A) -2: HJ500 (propylene homopolymer, MFR = 12, Samsung General Chemical)

(B) -1: CR-900 (trade name, tris (tribromo neopentyl) phosphate, Daihachi Chemical Industry)

(B) -2: S-102E (brand name, decabromo diphenyl ether, albermar)

(B) -3: S-8010 (brand name, bis pentabromo phenoxy ethane, Albermar)

(B) -4: PE-68 (trade name, tetrabromo bisphenol A-bis (2,3-dibromopropyl ether, great lake)

(B) -5: Nonnen 52 (Brand name, Bis [[3,5-Dibromo-4- (2 ', 3'-dibromopropyl okishi] phenyl] sulfonmarubishi)

(C): antimony trioxide Sb ₂ 0 ₃ W

(D) -1: Tinuvin-326 (brand name, 2- (3-t-butyl-5-methyl-2-hydroxydiphenyl) -5-chlorobenzotriazole, Ciba gygi)

(D) -2: Tinuvin-120 (trade name, 2,4-di-t-butylyl 3,5-di-t-butyl4-hydroxy benzoate, Ciba-Geigy)

(D) -3: Tinuvin-770 (Brand name, Bis (2,2,6,6-tetramethyl 4-piperidyl) sebacate, Ciba Guyi)

(D) -4: Cimasorb-944 (trade name, poly [[6- (1,1,3,3, -tetra methyl butyl) imino 1,3,5-diyl] [(2,2,6,6 , -Tetramethyl 4-piperidyl) imino]], Ciba-Geigi)

(D) -5: Cimasorb-119 (trade name, 1,3,5triazine-2,4,6-triamine, N`, N "`-[1,2-ethanetylbis [[[4.6-bis [Butyl (1,2,2,6,6-pentamethyl) imino] -1,3,5-triazin-2-yl] imino] -3,1 propaneyl]]-bis- [N` , N "-dibutyl-N`, N" -bis (1,2,2,6,6-pentamethyl-4-piperidyl) -shiba guigi)

(D) -6: CGL-116 (brand name, N-OR substituted hindered amine compound, Ciba-Geigi)

(D) -7: Tinuvin-123 (brand name, N-OR substituted hindered amine compound, Shiva kaigi)

As can be seen from the above, the flame-retardant polypropylene resin composition prepared according to the present invention has excellent light resistance and no discoloration properties as compared to conventional flame-retardant polypropylene resin compositions of UL94 V-0, V-1, V-2. It can be flame retardant. These characteristics can be obtained because of the low reactivity of tris (bromide neopentyl) phosphate with the hindered amine compound. In particular, the N-OR substituted hindered amine compound is N-hydrogen-type which does not have a nitrogen atom substituted. It is assumed that the basicity is much lower than that of the de amine compound.

Claims (4)

A flame retardant polyolefin resin composition comprising 100 parts by weight of polyolefin, 0.1 to 50 parts by weight of tris (neopentyl bromide) phosphate, 0.1 to 20 parts by weight of antimony trioxide, and 0.01 to 5 parts by weight of an N-OR substituted hindered amine compound. The flame retardant polyolefin resin composition according to claim 1, wherein the polyolefin is polypropylene. The tris (tribromo neopentyl) phosphate, tris (dibromo neopentyl) phosphate, and tris (monobromo neopentyl) phosphate according to claim 1, Flame retardant polyolefin resin composition, characterized in that at least one. The flame retardant polyolefin resin composition according to claim 1, wherein the N-OR substituted hindered amine compound is a substance having a structure represented by the following Chemical Formula 1. [Formula 1] [Formula 2]